Method of and apparatus for preserving ether



Jan.v l., 1929.

E. vMALLINczKRotar. JR., E'r A1.

METHOD 0F AND APPARATUS FOR PRESERVING ETHER Filed N ov. 17, 1927 WVWMl iii A y.

Patented Jan. '1, 1929.

UNE'TED Y EDWARD MALLINCKRODT, JR., OF ST. LOUIS, AND HENRY V. FARR, 0F FERGUSON, MIS- SOURI, ASSIGNORS T0 MALLINCKRODT CHEMICAL WORKS, OF ST. LOUIS, MIS- SOURI, A CORPORATION OF MISSOURI.

METHOD OF AND APPARATUS FOR PRESERVING ETHER.

Application filed Novembeijl?, 1927. Serial No. 233,980.

This invention relates to a method of, and apparatus for preserving ether, and with regard to certainy more specific features, toy a new and improved' package for ethyl ether.

Among the several objects of the invention may be noted the provision of means for protecting packaged ether from certain deterio-l rating iniuences exerted by the material comprising the original inner surface of the en closing package and the provision of n'ieans of the class described which are economical in application. Other objects will be in part o vious and in part pointed out hereinafter.

The invention accordingly comprises the elements and combinations of elements, fea-" tures of construction, arrangements of parts, materials andthe comblnationsof materials and the steps and sequence of steps, which -Will be exemplified in the following descrip- I tion and the application of which will be indicated in the annexed claims.

In the accompanying drawing', the figure lillustrates a cross section of a package for present invention has this invention. This previously used can was composed of conventional tin plate formed by the conventional process. During this process but after the tinning operation thereof, the plate passes through a bath of hot zinc chloride which removes dross and .oxides from the tin surface. Thereafter the sheet is flushed with hot palm oil, whereby mostof the zinc chloride is removed and the format-ion of an oxide film on the tin surface is substantially prevented. v

l/Ve have found that a clean tin surface, prepared for example by the above process and whether or not in the presence of iron, exerts what is thought to be a catalytic or accelerat ing effect upon the reaction between ethyl ether and air, whereby ethyl peroxide and/orl acetaldehyde is produced. i

The tin cans (of which those made by the abovei process are merely representative) when filled with ethyl ether, have been found in ether, and (3) lead. y

to exert the above cii'cct upon the formation of ethyl peroxide and/or acetaldehyde in the ether. The other, iillcd in cont-act with air, ca rrics with it sulicieut oxygen for the formation of these impurities, if thus catalyzed. Itv 1s conceivable that theveffect may be otherthan catalytic, but in any case the inventiony described herein is effective independently of the theory of chemical action exerted by the inner tin or similar .surface of the can. f

The presence. of ethyl peroxide and/or acetaldehydeis 4undesirable both in anaesthetic ether -and certain grades of commercial ether.

It ha's been found that the rate of spoilage depends upon the character and extent of the tin or other surface exposedI to the ether,

the rate of decomposition being a function of the'area of active tin. Hence, by cleaning the tin before the-,cans are used, the active catalytic surface is'exposed, to the detriment of the subsequei'itlypackaged ether. Even though the palm oil were not undesirable per se, and were left on the tin, the ether cuts through it and thereby permits the detrimental catalytic action of the tinto proceed.

It is to be understood that the above remarks, as well as those following, apply to cans made by the above process, or pure-tin cans 'or others having inner surfaces which,

are detrimental to the ether.

It has been proposed to overcome the detrimental catalytic action of the inner can surfaces by merely introducing into the container an alleged catalyst poison or anticatalyst.

On the other hand, the present invention comprises treating tin containers or similar x packages so that anon-catalytic (that is,

passive) surface is produced' on the inner face of the metal composing the can, said surface thus being devoid of objectionableA influence on the ether, whether the ether be 1n the presence or out of the presence of air. By the term non-catalytic we intend to include such materialsas (l) a film ofoxide of tin, (2) those varnishes which are insoluble Referring to the drawing, numeral 1 refers to the sheet iron which is surfaced on both sides with a coat of tin 3 and formed as a can or package 5.

Numeral 9 indicates the harmless inner passive surface. For the production of this surface several different methods of treatment have been found to be effective.

(l) The inner surface of the package, orl

the surface of the sheet material which is to become the inner surface, is treated by washing, dipping or otherwise applying a solution of one of the oxidizing substances, such as potassium permanganate, which has the effect of producing a passive surface on the tin. The result is that the possibility of catalytic or other detrimental action of the tin surface is eliminated'. It is preferable to have the entire inner surface of the package treated.

(2) The formation of a harmless surface may also be accomplished by oxidizing the surface in question by exposure to air or oxygen, preferably after having moistened the surface.

(3) oxidizing may also be accomplished by electrolysis.

y R. H. Bogue,

(4) Oxidation may be accomplished by heating the metal to an oxidizing temperature.

The treatment may also beeifected otherwise than by oxidation; for example,

'by applying varnishes (such as bakelite) which are insoluble in ether. Solutions of pyroxylin, cellulose acetate, and/or gelatin are also varnishes which on drying form a' film insoluble in ether; as .indicated in Pyroxylin Enamels and Lacquers by S. P.

Wilson, (1927, page. 29), The Technologyof Cellulose Esters by E. C. Worden, (1916, Vol. VIII, page 2670), and The Chemistry and Technolog of Gelatine and Glue by (6) Surfaces of harmless metals such as lead may also be applied by coating on the iron or tinned iron surface of the sheet material.

(7) Coatings of harmless metals may also be applied by electrolysis.

It will be seen from vthe above that one of the objects of the invention is to treat the inner surface of the can, so that there is substantially no catalytic or other action between the inner surface and the ether and/or air Within can, thus obviating the necessity for using preservatives or other foreign substances.

Furthermore, the invention eliminates the expense of a can composed completely of the non-detrimental substance and, at slight expense, makes the ordinary economical tin can available for packaging ether.

It is to be understood that the tinv or other plate may be treated in the manner described 1922, page 55), respectively.`

inside of the can is meant herein, at least the matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. v

We claim:

1. The etherF package comprising a metallic can having a tin oxide coating therein, said can containing ether.

2. A package of ether comprising a tin I can, a complete inner surface for said -can which is non-catalytic to ether and air placed in said can and a non-catalytic cap therefor,

said can containing ether.

3. A package of ether can, a non-metallic inner surface for said can comprising a tin' which is non-catalytic to ether and air placed A in said can and anon-detrimental cap therefor, said can containing ether.

4. A package of ether comprising a tin can and a completeA inner surface for said can which is non-catalytic to ether, said can containing ether;

5. A package of ether comprising a tincan and a complete inner surface for said) can .which is non-catalytic to ether and which is adapted to completely separate the tin of the can from contact with the contents thereof, said can containing ether.

6. A package of ether comprising a tin-can and a complete inner surface for said can which is non-catalytic to ether and ywhich is adapted to separate completely the tin of the can from contact with the contents thereof, said can containing ether. v

7. The method of packaging ether, which vcomprises treating metal for ethercontainers to form a surface thereon which is non-cata-y lytic .with 'respect to ether, forming, the container of said metal, and introducing ether therein. y

8. The method of packaging ether, which comprises treating metal for ether containers to form a surface thereon which is non-catalytic with respect to ether in the presence of air, forming the container of said metal, and introducing ether therein. c

9. The method of packaging ether, which comprises oxidizing the ent-ire tinned interior surfaces of the package, and introducing ether therein.

10. Ihe method of packagin ether, which comprises oxidizing the tinne interior surfaces of the package over such substantial areas as to prevent substantial deteriorating action by said surfaces on the ether, and in-V troducing ether therein.

11. The method of packaging ether, which comprises oxidizing the tinned interior surfaces of the package by means of the application thereto of potassium permanganate, and introducing ether therein.

12. The method of packaging ether, which comprises oxidizing the tinned interior surfaces of the package by means of the application thereto of an oxidizing salt, and introducing ether therein.

13. The method of packaging ether, which comprises treating tin plate for contact with the ether by producing on the tin surface of the platea lilm Which is non-catalytic to peroxide formation in the ether, and introducing ether into a package made of said plate.

14. The method of packaging ether, which comprises treating tin plate for contact with the ether by producing on the tin surface of the plate a film which is non-catalytic to peroxide formation in thc ether, said film having an extent Which is substantially equal to the normal extent of contact of the ether with the package, and introducing ether into a package made of said plate.

15. The method of packaging ether, which comprises oxidizing the entire tinned interior surfaces of the package by contacting said surfaces with an oxidizing material, drying the package, and introducing ether into the package.

In testimony whereof, We have signed our names to this specification this 12th day of November, 1927.

EDWARD MALLINCKRODT, JR. HENRY V. FARB. 

